scholarly journals Seasonal variability of atmospheric nitrogen oxides and non-methane hydrocarbons at the GEOSummit station, Greenland

2015 ◽  
Vol 15 (12) ◽  
pp. 6827-6849 ◽  
Author(s):  
L. J. Kramer ◽  
D. Helmig ◽  
J. F. Burkhart ◽  
A. Stohl ◽  
S. Oltmans ◽  
...  
Keyword(s):  
Nitrogen Oxides ◽  
Biomass Burning ◽  
Atmospheric Chemistry ◽  
Seasonal Variability ◽  
The Arctic ◽  
Atmospheric Nitrogen ◽  
Alkyl Nitrates ◽  
Data Set ◽  
Air Masses ◽  
The Impact

Abstract. Measurements of atmospheric nitrogen oxides NOx (NOx = NO + NO2), peroxyacetyl nitrate (PAN), NOy, and non-methane hydrocarbons (NMHC) were taken at the Greenland Environmental Observatory at Summit (GEOSummit) station, Greenland (72.34° N, 38.29° W; 3212 m a.s.l.), from July 2008 to July 2010. The data set represents the first year-round concurrent record of these compounds sampled at a high latitude Arctic site. Here, the study focused on the seasonal variability of these important ozone (O3) precursors in the Arctic troposphere and the impact from transported anthropogenic and biomass burning emissions. Our analysis shows that PAN is the dominant NOy species in all seasons at Summit, varying from 42 to 76 %; however, we find that odd NOy species (odd NOy = NOy − PAN − NOx) contribute a large amount to the total NOy speciation. We hypothesize that the source of this odd NOy is most likely alkyl nitrates and nitric acid (HNO3) from transported pollution, and photochemically produced species such as nitrous acid (HONO). FLEXPART retroplume analyses and black carbon (BC) tracers for anthropogenic and biomass burning (BB) emissions were used to identify periods when the site was impacted by polluted air masses. Europe contributed the largest source of anthropogenic emissions during the winter months (November–March) with 56 % of the total anthropogenic BC tracer originating from Europe in 2008–2009 and 69 % in 2009–2010. The polluted plumes resulted in mean enhancements above background levels up to 334, 295, 88, and 1119 pmol mol−1 for NOy, PAN, NOx, and ethane, respectively, over the two winters. Enhancements in O3 precursors during the second winter were typically higher, which may be attributed to the increase in European polluted air masses transported to Summit in 2009–2010 compared to 2008–2009. O3 levels were highly variable within the sampled anthropogenic plumes with mean ΔO3 levels ranging from −6.7 to 7.6 nmol mol−1 during the winter periods. North America was the primary source of biomass burning emissions during the summer; however, only 13 BB events were observed as the number of air masses transported to Summit, with significant BB emissions, was low in general during the measurement period. The BB plumes were typically very aged, with median transport times to the site from the source region of 14 days. The analyses of O3 and precursor levels during the BB events indicate that some of the plumes sampled impacted the atmospheric chemistry at Summit, with enhancements observed in all measured species.

scholarly journals Seasonal variability of atmospheric nitrogen oxides and non-methane hydrocarbons at the GEOSummit station, Greenland

2014 ◽  
Vol 14 (9) ◽  
pp. 13817-13867 ◽  
Author(s):  
L. J. Kramer ◽  
D. Helmig ◽  
J. F. Burkhart ◽  
A. Stohl ◽  
S. Oltmans ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Seasonal Variability ◽  
Lower Troposphere ◽  
The Arctic ◽  
Free Troposphere ◽  
Alkyl Nitrates ◽  
Data Set ◽  
Air Masses ◽  
Background Levels ◽  
The Impact

Abstract. Measurements of atmospheric NOx (NOx = NO + NO2), peroxyacetyl nitrate (PAN), NOy and non-methane hydrocarbons (NMHC) were taken at the GEOSummit Station, Greenland (72.34° N, 38.29° W, 3212 m.a.s.l) from July 2008 to July 2010. The data set represents the first year-round concurrent record of these compounds sampled at a high latitude Arctic site in the free troposphere. Here, the study focused on the seasonal variability of these important ozone (O3) precursors in the Arctic free troposphere and the impact from transported anthropogenic and biomass burning emissions. Our analysis shows that PAN is the dominant NOy species in all seasons at Summit, varying from 49% to 78%, however, we find that odd NOy species (odd NOy = NOy − PAN-NOx) contribute a large amount to the total NOy speciation with monthly means of up to 95 pmol mol−1 in the winter and ∼40 pmol mol−1 in the summer, and that the level of odd NOy species at Summit during summer is greater than that of NOx. We hypothesize that the source of this odd NOy is most likely alkyl nitrates from transported pollution, and photochemically produced species such as HNO3 and HONO. FLEXPART retroplume analysis and tracers for anthropogenic and biomass burning emissions, were used to identify periods when the site was impacted by polluted air masses. Europe contributed the largest source of anthropogenic emissions during the winter and spring months, with up to 82% of the simulated anthropogenic black carbon originating from this region between December 2009 and March 2010, whereas, North America was the primary source of biomass burning emissions. Polluted air masses were typically aged, with median transport times to the site from the source region of 11 days for anthropogenic events in winter, and 14 days for BB plumes. Overall we find that the transport of polluted air masses to the high altitude Arctic typically resulted in high variability in levels of O3 and O3 precursors. During winter, plumes originating from mid-latitude regions and transported in the lower troposphere to Summit often result in lower O3 mole fractions than background levels. However, plumes transported at higher altitudes can result in positive enhancements in O3 levels. It is therefore likely that the air masses transported in the mid-troposphere were mixed with air from stratospheric origin. Similar enhancements in O3 and its precursors were also observed during periods when FLEXPART indicated that biomass burning emissions impacted Summit. The analysis of anthropogenic events over summer show that emissions of anthropogenic origin have a greater impact on O3 and precursor levels at Summit than biomass burning sources during the measurement period, with enhancements above background levels of up to 16 nmol mol−1 for O3 and 237 pmol mol−1 and 205 pmol mol−1, 28 pmol mol−1 and 1.0 nmol mol−1 for NOy, PAN, NOx and ethane, respectively.

scholarly journals Ozone and carbon monoxide observations over open oceans on R/V <i>Mirai</i> from 67° S to 75° N during 2012 to 2017: Testing global chemical reanalysis in terms of Arctic processes, low ozone levels at low latitudes, and pollution transport

2019 ◽  
Author(s):  
Yugo Kanaya ◽  
Kazuyuki Miyazaki ◽  
Fumikazu Taketani ◽  
Takuma Miyakawa ◽  
Hisahiro Takashima ◽  
...  
Keyword(s):  
Carbon Monoxide ◽  
Atmospheric Chemistry ◽  
Critical Evaluation ◽  
Chemical Transport ◽  
Tropospheric Chemistry ◽  
Set Covering ◽  
The Arctic ◽  
Pollution Transport ◽  
Data Set ◽  
Air Masses

Abstract. Constraints from ozone (O3) observations over oceans are needed in addition to those from terrestrial regions to fully understand global tropospheric chemistry and its impact on the climate. Here, we provide a large data set of ozone and carbon monoxide (CO) levels observed (for 11 666 and 10 681 h, respectively) over oceans. The data set is derived from observations made during 24 research cruise legs of R/V Mirai during 2012 to 2017, in the Southern, Indian, Pacific, and Arctic Oceans, covering the region from 67° S to 75° N. The data are suitable for critical evaluation of the over-ocean distribution of ozone derived from chemical transport models. We first give an overview of the statistics in the data set and highlight key features in terms of geographical distribution and air mass type. We then use the data set to evaluate ozone concentration fields from Tropospheric Chemistry Reanalysis version 2 (TCR-2), produced by assimilating a suite of satellite observations of multiple species into a chemical transport model, namely CHASER. For long-range transport of polluted air masses from continents to the oceans, during which the effects of forest fires and fossil fuel combustion were recognized, TCR-2 gave an excellent performance in reproducing the observed temporal variations and photochemical buildup of O3 when assessed from ΔO3 / ΔCO ratios. For clean marine conditions with low and stable CO concentrations, two focused analyses were performed. The first was in the Arctic (> 70° N) in September every year from 2013 to 2016; TCR-2 underpredicted O3 levels by 6.7 ppb (21 %) on average. The observed vertical profiles from O3 soundings from R/V Mirai during September 2014 had less steep vertical gradients at low altitudes (> 850 hPa) than those obtained TCR-2. This suggests the possibilities of more efficient descent of the O3-rich air from above or less efficient dry deposition on the surface than were assumed in the model. In the second analysis, over the western Pacific equatorial region (125–165° E, 10° S to 25° N), the observed O3 level frequently decreased to less than 10 ppb in comparison to that obtained with TCR-2, and also those obtained in most of the Atmospheric Chemistry Climate Model Intercomparison Project (ACCMIP) model runs for the decade from 2000. These results imply loss processes that are unaccounted for in the models. We found that the model’s positive bias positively correlated with the daytime residence times of air masses over a particular grid, namely 165–180° E and 15–30° N; an additional loss rate of 0.25 ppb h−1 in the grid best explained the gap. Halogen chemistry, which is commonly omitted from currently used models, might be active in this region and could have contributed to additional losses. Our open data set covering wide ocean regions is complementary to the Tropospheric Ozone Assessment Report data set, which basically comprises ground-based observations, and enables a fully global study of the behavior of O3.

scholarly journals Reactive nitrogen, ozone and ozone production in the Arctic troposphere and the impact of stratosphere-troposphere exchange

2011 ◽  
Vol 11 (24) ◽  
pp. 13181-13199 ◽  
Author(s):  
Q. Liang ◽  
J. M. Rodriguez ◽  
A. R. Douglass ◽  
J. H. Crawford ◽  
J. R. Olson ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Stratospheric Ozone ◽  
Arctic Region ◽  
Ozone Production ◽  
The Arctic ◽  
Subsequent Formation ◽  
Air Masses ◽  
Upper Troposphere ◽  
Mixing Ratios ◽  
The Impact

Abstract. We use aircraft observations obtained during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission to examine the distributions and source attributions of O3 and NOy in the Arctic and sub-Arctic region. Using a number of marker tracers, we distinguish various air masses from the background troposphere and examine their contributions to NOx, O3, and O3 production in the Arctic troposphere. The background Arctic troposphere has a mean O3 of ~60 ppbv and NOx of ~25 pptv throughout spring and summer with CO decreasing from ~145 ppbv in spring to ~100 ppbv in summer. These observed mixing ratios are not notably different from the values measured during the 1988 ABLE-3A and the 2002 TOPSE field campaigns despite the significant changes in emissions and stratospheric ozone layer in the past two decades that influence Arctic tropospheric composition. Air masses associated with stratosphere-troposphere exchange are present throughout the mid and upper troposphere during spring and summer. These air masses, with mean O3 concentrations of 140–160 ppbv, are significant direct sources of O3 in the Arctic troposphere. In addition, air of stratospheric origin displays net O3 formation in the Arctic due to its sustainable, high NOx (75 pptv in spring and 110 pptv in summer) and NOy (~800 pptv in spring and ~1100 pptv in summer). The air masses influenced by the stratosphere sampled during ARCTAS-B also show conversion of HNO3 to PAN. This active production of PAN is the result of increased degradation of ethane in the stratosphere-troposphere mixed air mass to form CH3CHO, followed by subsequent formation of PAN under high NOx conditions. These findings imply that an adequate representation of stratospheric NOy input, in addition to stratospheric O3 influx, is essential to accurately simulate tropospheric Arctic O3, NOx and PAN in chemistry transport models. Plumes influenced by recent anthropogenic and biomass burning emissions observed during ARCTAS show highly elevated levels of hydrocarbons and NOy (mostly in the form of NOx and PAN), but do not contain O3 higher than that in the Arctic tropospheric background except some aged biomass burning plumes sampled during spring. Convection and/or lightning influences are negligible sources of O3 in the Arctic troposphere but can have significant impacts in the upper troposphere in the continental sub-Arctic during summer.

scholarly journals Reactive nitrogen, ozone and ozone production in the Arctic troposphere and the impact of stratosphere-troposphere exchange

2011 ◽  
Vol 11 (4) ◽  
pp. 10721-10767 ◽  
Author(s):  
Q. Liang ◽  
J. M. Rodriguez ◽  
A. R. Douglass ◽  
J. H. Crawford ◽  
E. Apel ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Arctic Region ◽  
Tropospheric Chemistry ◽  
Ozone Production ◽  
The Arctic ◽  
Source Attribution ◽  
Air Masses ◽  
Upper Troposphere ◽  
Mixing Ratios ◽  
The Impact

Abstract. We analyze the aircraft observations obtained during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellite (ARCTAS) mission together with the GEOS-5 CO simulation to examine O3 and NOy in the Arctic and sub-Arctic region and their source attribution. Using a number of marker tracers and their probability density distributions, we distinguish various air masses from the background troposphere and examine their contribution to NOx, O3, and O3 production in the Arctic troposphere. The background Arctic troposphere has mean O3 of ~60 ppbv and NOx of ~25 pptv throughout spring and summer with CO decreases from ~145 ppbv in spring to ~100 ppbv in summer. These observed CO, NOx and O3 mixing ratios are not notably different from the values measured during the 1988 ABLE-3A and the 2002 TOPSE field campaigns despite the significant changes in the past two decades in processes that could have changed the Arctic tropospheric composition. Air masses associated with stratosphere-troposphere exchange are present throughout the mid and upper troposphere during spring and summer. These air masses with mean O3 concentration of 140–160 ppbv are the most important direct sources of O3 in the Arctic troposphere. In addition, air of stratospheric origin is the only notable driver of net O3 formation in the Arctic due to its sustainable high NOx (75 pptv in spring and 110 pptv in summer) and NOy (~800 pptv in spring and ~1100 pptv in summer) levels. The ARCTAS measurements present observational evidence suggesting significant conversion of nitrogen from HNO3 to NOx and then to PAN (a net formation of ~120 pptv PAN) in summer when air of stratospheric origin is mixed with tropospheric background during stratosphere-to-troposphere transport. These findings imply that an adequate representation of stratospheric O3 and NOy input are essential in accurately simulating O3 and NOx photochemistry as well as the atmospheric budget of PAN in tropospheric chemistry transport models of the Arctic. Anthropogenic and biomass burning pollution plumes observed during ARCTAS show highly elevated hydrocarbons and NOy (mostly in the form of NOx and PAN), but do not contribute significantly to O3 in the Arctic troposphere except in some of the aged biomass burning plumes sampled during spring. Convection and/or lightning influences are negligible sources of O3 in the Arctic troposphere but can have significant impacts in the upper troposphere in the continental sub-Arctic during summer.

scholarly journals Observations of peroxyacetyl nitrate (PAN) in the upper troposphere by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS)

2013 ◽  
Vol 13 (1) ◽  
pp. 1575-1607 ◽  
Author(s):  
K. A. Tereszchuk ◽  
D. P. Moore ◽  
J. J. Harrison ◽  
C. D. Boone ◽  
M. Park ◽  
...  
Keyword(s):  
Fourier Transform ◽  
Biomass Burning ◽  
Atmospheric Chemistry ◽  
Lower Stratosphere ◽  
Fourier Transform Spectrometer ◽  
Data Set ◽  
Upper Troposphere ◽  
Volatile Organic ◽  
The Impact ◽  
Chemistry Experiment

Abstract. Peroxyacetyl nitrate (CH3CO·O2NO2, abbreviated as PAN) is a trace molecular species present in the troposphere and lower stratosphere due primarily to pollution from fuel combustion and the pyrogenic outflows from biomass burning. In the lower troposphere, PAN has a relatively short life-time and is principally destroyed within a few hours through thermolysis, but it can act as a reservoir and carrier of NOx in the colder temperatures of the upper troposphere where UV photolysis becomes the dominant loss mechanism. Pyroconvective updrafts from large biomass burning events can inject PAN into the upper troposphere and lower stratosphere (UTLS), providing a means for the long-range transport of NOx. Given the extended lifetimes at these higher altitudes, PAN is readily detectable via satellite remote sensing. A new PAN data product is now available for the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) Version 3.0 data set. We report measurements of PAN in Boreal biomass burning plumes recorded during the Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS) campaign. The retrieval method employed and errors analysis are described in full detail. The retrieved volume mixing ratio (VMR) profiles are compared to coincident measurements made by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument on the European Space Agency (ESA) ENVIronmental SATellite (ENVISAT). Three ACE-FTS occultations containing measurements of Boreal biomass burning outflows, recorded during BORTAS, were identified as having coincident measurements with MIPAS. In each case, the MIPAS measurements demonstrated good agreement with the ACE-FTS VMR profiles for PAN. The ACE-FTS PAN data set is used to obtain zonal mean distributions of seasonal averages from ~5 to 20 km. A strong seasonality is clearly observed for PAN concentrations in the global UTLS. Since the principal source of PAN in the UTLS is due to lofted biomass burning emissions from the pyroconvective updrafts created by large fires, the observed seasonality in enhanced PAN coincides with fire activity in different geographical regions throughout the year. This work is part of an in-depth investigation that is being conducted in an effort to study the aging and chemical evolution of biomass burning emissions in the UTLS by remote, space-borne measurements made by ACE-FTS to further our understanding of the impact of pyrogenic emissions on atmospheric chemistry. Included in this study will be the addition of new, pyrogenic, volatile organic hydrocarbons (VOCs) and oxygenated volatile organic compounds (OVOCs) to expand upon the already extensive suite of molecules retrieved by ACE-FTS to aid in elucidating biomass burning plume chemistry in the free troposphere.

scholarly journals The NO<sub><i>x</i></sub> dependence of bromine chemistry in the Arctic atmospheric boundary layer

2015 ◽  
Vol 15 (18) ◽  
pp. 10799-10809 ◽  
Author(s):  
K. D. Custard ◽  
C. R. Thompson ◽  
K. A. Pratt ◽  
P B. Shepson ◽  
J. Liao ◽  
...  
Keyword(s):  
Climate Change ◽  
Boundary Layer ◽  
Nitrogen Oxides ◽  
Sea Ice ◽  
Gas Phase ◽  
Atmospheric Chemistry ◽  
The Arctic ◽  
Arctic Boundary Layer ◽  
Large Variability ◽  
The Impact

Abstract. Arctic boundary layer nitrogen oxides (NOx = NO2 + NO) are naturally produced in and released from the sunlit snowpack and range between 10 to 100 pptv in the remote background surface layer air. These nitrogen oxides have significant effects on the partitioning and cycling of reactive radicals such as halogens and HOx (OH + HO2). However, little is known about the impacts of local anthropogenic NOx emission sources on gas-phase halogen chemistry in the Arctic, and this is important because these emissions can induce large variability in ambient NOx and thus local chemistry. In this study, a zero-dimensional photochemical kinetics model was used to investigate the influence of NOx on the unique springtime halogen and HOx chemistry in the Arctic. Trace gas measurements obtained during the 2009 OASIS (Ocean – Atmosphere – Sea Ice – Snowpack) field campaign at Barrow, AK were used to constrain many model inputs. We find that elevated NOx significantly impedes gas-phase halogen radical-based depletion of ozone, through the production of a variety of reservoir species, including HNO3, HO2NO2, peroxyacetyl nitrate (PAN), BrNO2, ClNO2 and reductions in BrO and HOBr. The effective removal of BrO by anthropogenic NOx was directly observed from measurements conducted near Prudhoe Bay, AK during the 2012 Bromine, Ozone, and Mercury Experiment (BROMEX). Thus, while changes in snow-covered sea ice attributable to climate change may alter the availability of molecular halogens for ozone and Hg depletion, predicting the impact of climate change on polar atmospheric chemistry is complex and must take into account the simultaneous impact of changes in the distribution and intensity of anthropogenic combustion sources. This is especially true for the Arctic, where NOx emissions are expected to increase because of increasing oil and gas extraction and shipping activities.

scholarly journals Ozone photochemistry in boreal biomass burning plumes

2013 ◽  
Vol 13 (15) ◽  
pp. 7321-7341 ◽  
Author(s):  
M. Parrington ◽  
P. I. Palmer ◽  
A. C. Lewis ◽  
J. D. Lee ◽  
A. R. Rickard ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Forest Fires ◽  
Dynamic Range ◽  
Ozone Production ◽  
The Arctic ◽  
Aircraft Measurements ◽  
Alkyl Nitrates ◽  
Mixing Ratios ◽  
Aerosol Loading ◽  
The Impact

Abstract. We present an analysis of ozone (O3) photochemistry observed by aircraft measurements of boreal biomass burning plumes over eastern Canada in the summer of 2011. Measurements of O3 and a number of key chemical species associated with O3 photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the "quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS) experiment between 12 July and 3 August 2011. The location and timing of the aircraft measurements put BORTAS into a unique position to sample biomass burning plumes from the same source region in Northwestern Ontario with a range of ages. We found that O3 mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (= NOy-NOx) revealed that the potential for O3 production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 10 days. The BORTAS measurements provided a wide dynamic range of O3 production in the sampled biomass burning plumes with ΔO3/ΔCO enhancement ratios increasing from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. We found that the main contributing factor to the variability in the ΔO3/ΔCO enhancement ratio was ΔCO in plumes with photochemical ages less than 4 days, and that was a transition to ΔO3 becoming the main contributing factor in plumes with ages greater than 4 days. In comparing O3 mixing ratios with components of the NOy budget, we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiency (OPE) of 7.7 ± 3.5 ppbv ppbv−1 relative to ΣAN and 1.6 ± 0.9 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, OPE increased to 472 ± 28 ppbv ppbv−1 relative to ΣAN and 155 ± 5 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and O3 production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to O3. The BORTAS measurements of O3 photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the Troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.

scholarly journals Ozone and carbon monoxide observations over open oceans on R/V <i>Mirai</i> from 67° S to 75° N during 2012 to 2017: testing global chemical reanalysis in terms of Arctic processes, low ozone levels at low latitudes, and pollution transport

2019 ◽  
Vol 19 (11) ◽  
pp. 7233-7254 ◽  
Author(s):  
Yugo Kanaya ◽  
Kazuyuki Miyazaki ◽  
Fumikazu Taketani ◽  
Takuma Miyakawa ◽  
Hisahiro Takashima ◽  
...  
Keyword(s):  
Carbon Monoxide ◽  
Atmospheric Chemistry ◽  
Forest Fires ◽  
Critical Evaluation ◽  
Tropospheric Chemistry ◽  
Set Covering ◽  
The Arctic ◽  
Pollution Transport ◽  
Data Set ◽  
Air Masses

Abstract. Constraints from ozone (O3) observations over oceans are needed in addition to those from terrestrial regions to fully understand global tropospheric chemistry and its impact on the climate. Here, we provide a large data set of ozone and carbon monoxide (CO) levels observed (for 11 666 and 10 681 h, respectively) over oceans. The data set is derived from observations made during 24 research cruise legs of R/V Mirai during 2012 to 2017, in the Southern, Indian, Pacific, and Arctic oceans, covering the region from 67∘ S to 75∘ N. The data are suitable for critical evaluation of the over-ocean distribution of ozone derived from global atmospheric chemistry models. We first give an overview of the statistics in the data set and highlight key features in terms of geographical distribution and air mass type. We then use the data set to evaluate ozone mixing ratio fields from the tropospheric chemistry reanalysis version 2 (TCR-2), produced by assimilating a suite of satellite observations of multiple species into a global atmospheric chemistry model, namely CHASER. For long-range transport of polluted air masses from continents to the oceans, during which the effects of forest fires and fossil fuel combustion were recognized, TCR-2 gave an excellent performance in reproducing the observed temporal variations and photochemical buildup of O3 when assessed from ΔO3∕ΔCO ratios. For clean marine conditions with low and stable CO mixing ratios, two focused analyses were performed. The first was in the Arctic (> 70∘ N) in September every year from 2013 to 2016; TCR-2 underpredicted O3 levels by 6.7 ppbv (21 %) on average. The observed vertical profiles from O3 soundings from R/V Mirai during September 2014 had less steep vertical gradients at low altitudes (> 850 hPa) than those obtained by TCR-2. This suggests the possibility of a more efficient descent of the O3-rich air from above than assumed in the models. For TCR-2 (CHASER), dry deposition on the Arctic ocean surface might also have been overestimated. In the second analysis, over the western Pacific equatorial region (125–165∘ E, 10∘ S to 25∘ N), the observed O3 level more frequently decreased to less than 10 ppbv in comparison to that obtained with TCR-2 and also those obtained in most of the Atmospheric Chemistry Climate Model Intercomparison Project (ACCMIP) model runs for the decade from 2000. These results imply loss processes that are unaccounted for in the models. We found that the model's positive bias positively correlated with the daytime residence times of air masses over a particular grid, namely 165–180∘ E and 15–30∘ N; an additional loss rate of 0.25 ppbv h−1 in the grid best explained the gap. Halogen chemistry, which is commonly omitted from currently used models, might be active in this region and could have contributed to additional losses. Our open data set covering wide ocean regions is complementary to the Tropospheric Ozone Assessment Report data set, which basically comprises ground-based observations and enables a fully global study of the behavior of O3.

scholarly journals The NO<sub>x</sub> dependence of bromine chemistry in the Arctic atmospheric boundary layer

2015 ◽  
Vol 15 (6) ◽  
pp. 8329-8360 ◽  
Author(s):  
K. D. Custard ◽  
C. R. Thompson ◽  
K. A. Pratt ◽  
P. B. Shepson ◽  
J. Liao ◽  
...  
Keyword(s):  
Climate Change ◽  
Boundary Layer ◽  
Nitrogen Oxides ◽  
Sea Ice ◽  
Gas Phase ◽  
Atmospheric Chemistry ◽  
The Arctic ◽  
Arctic Boundary Layer ◽  
Large Variability ◽  
The Impact

Abstract. Arctic boundary layer nitrogen oxides (NOx = NO2 + NO) are naturally produced in and released from the sunlit snowpack and range between 10 to 100 pptv in the remote background surface layer air. These nitrogen oxides have significant effects on the partitioning and cycling of reactive radicals such as halogens and HOx (OH + HO2). However, little is known about the impacts of local anthropogenic NOx emission sources on gas-phase halogen chemistry in the Arctic, and this is important because these emissions can induce large variability in ambient NOx and thus local chemistry. In this study, a zero-dimensional photochemical kinetics model was used to investigate the influence of NOx on the unique springtime halogen and HOx chemistry in the Arctic. Trace gas measurements obtained during the 2009 OASIS (Ocean–Atmosphere–Sea Ice–Snowpack) field campaign at Barrow, AK were used to constrain many model inputs. We find that elevated NOx significantly impedes gas-phase radical chemistry, through the production of a variety of reservoir species, including HNO3, HO2NO2, peroxyacetyl nitrate (PAN), BrNO2, ClNO2 and reductions in BrO and HOBr, with a concomitant, decreased net O3 loss rate. The effective removal of BrO by anthropogenic NOx was directly observed from measurements conducted near Prudhoe Bay, AK during the 2012 Bromine, Ozone, and Mercury Experiment (BROMEX). Thus, while changes in snow-covered sea ice attributable to climate change may alter the availability of molecular halogens for ozone and Hg depletion, predicting the impact of climate change on polar atmospheric chemistry is complex and must take into account the simultaneous impact of changes in the distribution and intensity of anthropogenic combustion sources. This is especially true for the Arctic, where NOx emissions are expected to increase because of increasing oil and gas extraction and shipping activities.

scholarly journals Ozone photochemistry in boreal biomass burning plumes

2013 ◽  
Vol 13 (1) ◽  
pp. 1795-1853 ◽  
Author(s):  
M. Parrington ◽  
P. I. Palmer ◽  
A. C. Lewis ◽  
J. D. Lee ◽  
A. R. Rickard ◽  
...  
Keyword(s):  
Biomass Burning ◽  
Forest Fires ◽  
Ozone Production ◽  
The Arctic ◽  
Aircraft Measurements ◽  
Alkyl Nitrates ◽  
Mixing Ratios ◽  
Aerosol Loading ◽  
Ozone Photochemistry ◽  
The Impact

Abstract. We present an analysis of ozone photochemistry observed by aircraft measurements of boreal biomass burning plumes over Eastern Canada in the summer of 2011. Measurements of ozone and a number of key chemical species associated with ozone photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the quantifying the impact of BOReal forest fires on tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS) experiment between 12 July and 3 August 2011. We found that ozone mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (=NOy - NOx) revealed that the potential for ozone production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 15 days. Ozone production, calculated from ΔO3/ΔCO enhancement ratios, increased from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. In comparing ozone mixing ratios with components of the NOy budget we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiencies of 8 ppbv ppbv−1 relative to ΣAN and 2 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, ozone production efficiency increased to 473 ppbv ppbv−1 relative to ΣAN and 155 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and ozone production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to ozone. The BORTAS measurements of ozone photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.

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